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Module 3: Liquid Fossil Fuel (Petroleum)
Lecture 20: Secondary Processing












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Keywords: Thermal cracking, visbreaking, hydrocracking, naphtha

3.4 Secondary processing
3.4.1 Cracking
Cracking is a secondary process in the refinery where change in composition of the petroleum
fractions is done by the action of heat alone (thermal cracking) or heat in presence of a catalyst
(catalytic cracking). Cracking is the decomposition of C-C bond of hydrocarbon molecules. The
primary or first stage products of cracking are lower molecular weight compounds than the feed
and are mainly olefinic in nature. The second stage products come from the reactions like
isomerisation, cyclisation, polymerization etc. of primary products in-situ. These secondary
products may be of the same molecular weight or higher than the feedstock. The fundamental
difference between thermal cracking and catalytic cracking is that, the former proceeds via free-
radical mechanism while the latter occurs mainly by a carbocation mechanism. Hydrocracking is
the cracking operation where hydrogen is introduced during cracking; hence it is a combination
of hydrogenation and cracking.
Thermal cracking
Thermal cracking was first commercialized in 1912 to increase the yield of middle distillate
fractions (which boil in the range of 150-350
0
C) from crude oil. Visbreaking is a mild thermal
cracking operation which improves the viscosity of a heavy fraction (boiling range >250
0
C) by a
non-severe route. Coking is a severe thermal cracking operation whose target is to maximize
coke production from a heavy stock along with gas, gasoline and middle distillate. Although
thermal cracking is not practiced in most modern refinery and is replaced by catalytic cracking
yet there is some importance of thermal cracking depending on the products required or aimed.
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Table 1 shows the thermal cracking temperature range and the corresponding products obtained
thereof.
Table 1. Thermal cracking processes
___________________________________________________________________________
Cracking temperature (
0
C) Name of the process Products
___________________________________________________________________________
425-460 Visbreaking Fuel oil
460-520 Thermal cracking Gas, gasoline, fuel oil
520-600 Low temperature coking Gas, gasoline, soft coke
600-800 Gas production Gas and unsaturated
800-1000 High temperature coking Gas, heavy aromatics, pitch, coke
Above 1000 Decomposition H
2
, gas, carbon black
___________________________________________________________________________

However, thermal cracking is indispensible as it is a source of primary petrochemical products,
i.e ethylene, which is produced by thermal cracking of straight run naphtha and gas-oils and this
process, is called steam cracking.
Visbreaking
Visbreaking is a mild thermal cracking process utilized in the refinery to reduce the viscosity
and/or improve the pour point of a heavy oil, mainly residues, AR and VR both. A typical
visbreaker unit is shown in Fig. 1. In this process, the residual oil is heated at a desired
temperature in a furnace and then rapidly transferred to a soaking drum, where, cracking occurs
for a desired residence time up to the desired degree of cracking. The cracked products are
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quenched immediately by exchanging heat with gasoil or cold visbroken tar to stop the cracking
reaction then and there and prevent coking thereby. This type of visbreaking is called a soaker
type visbreaking. In this type, the cracking reactions are initiated in the furnace but the progress
of the reactions take place in the soaker drum.
Another type of visbreaking operation is coil type, where, the cracking reactions occur in the
furnace coil. Here the residence time of the reactions are kept as short as possible to avoid much
coking. A long coil is normally used to complete the desired degree of reaction. The cracking
temperature used in soaker type is normally lesser than that of coil type and hence, the coke
deposition is also less in case of the former one.

Fig.1. Visbreaker unit
The products obtained from visbreaking are gas, middle distillates and stable fuel oil.
Visbreaking is often used to increase the middle distillate yield in the refinery by reducing the
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amount of heavy oil or bottom of the barrel (residual oil). This distillate fraction is used as a
blending agent of fuel oil to reduce its viscosity. This distillate replaces diesel in refinery which
is actually used as the blending agent. Hence, economics is strongly driven by the benefit of
distillate production and the cost of visbreaking.
Hydrocracking
Hydrocracking is an operation in which low-value gas oil with a high percentage of polynuclear
aromatics is simultaneously cracked and hydrogenated to produce low-boiling and mid-boiling
distillates which are of high value. The primary advantage of hydrocracking is that, it selectively
produces gasoline, diesel fuel or jet fuel by cracking and hydrogenation of polyaromatics,
without producing any unwanted low molecular weight gases. The first modern hydrocracking
unit was developed by Chevron in 1959 which is known as Chevron Isocracking Process.
Hydrocracking is widely accepted by the refiners because of its ability to produce high quality
products. Except gasoline and middle distillate this process gives lube oil base stocks and heavy
oil suitable as the feedstock for catalytic cracking. A flow diagram of hydrocracking unit is
shown in Fig. 2.
Light coker gas oils and light cycle oils were used as feedstocks for hydrocracking earlier, but as
the technology is improved, industry can take up heavier straight run vacuum gas oil, coker gas
oil and solvent deasphalted oils as the feed for the process. Hydrocarcking feedstocks are
complex mixtures of mainly paraffins, naphthenes and aromatics. The boiling range is 345
0
C+.
As the feedstock is passed through the reactor, aromatics are the first components to react;
mainly forming naphthenes, which boil in the same range of 345
0
C+. Hence the amount of
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naphthenes of the same range increases. After most of the aromatics are converted to naphthenes,
the naphthenes start to crack and the boiling point drops below 345
0
C.

Fig. 2. Flow diagram of hydrocracking unit
Paraffins donot show significant cracking reaction in this single pass operation. Hydrocracking
reactions are inhibited by the presence of nitrogen and sulphur compounds. Those compounds
are mostly removed by this process when nitrogen compounds are converted to ammonia and
sulphur compounds are converted to hydrogen sulfide. Conversion of sulphur compounds is
easier than the nitrogen ones, as the former requires lesser hydrogen partial pressure. A
precaution should be made in recycled hydrogen gas which should be free from any
contamination of ammonia.
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Hydrocracking can be done either thermally or catalytically, but the most common
hydrocracking is catalytic. Hydrocracking catalysts mainly consist of active metals on solid acid
supports where the acidic part of the catalyst serves the cracking function and the hydrogenation
function is provided by the metals. The acidic supports are mainly amorphous silica-alumina,
crystalline zeolite or a mixture of two. The metals that are used for performing hydrogenation
are palladium, platinum, molybdenum, tungsten, cobalt or nickel.











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Reference:
1. Modern Petroleum Refining Processes, B.K.B.Rao, 4
th
Ed.,Oxford & IBH Publishing Co. Ltd.
2002.
2. Modern petroleum technology, Downstream, ed. by Alan G, Lucas, Vol 2, 6
th
edition, IP, J ohn
Wiley & Sons Ltd., 2001.
3. Petroleum Refining Processes, J ames G. Speight and Baki Ozum, Marcel Dekker Inc, ISBN:
0-8247-0599-8 (Print Edition).